CN105683172A - Process To Produce Terephthalic Acid - Google Patents

Process To Produce Terephthalic Acid Download PDF

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CN105683172A
CN105683172A CN201480059762.7A CN201480059762A CN105683172A CN 105683172 A CN105683172 A CN 105683172A CN 201480059762 A CN201480059762 A CN 201480059762A CN 105683172 A CN105683172 A CN 105683172A
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furan
replacement
ethylene
cycloaddition
represented
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CN105683172B (en
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曹光
J·R·莱特纳
J·古兹曼
S·L·罗
G·D·默尔
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ExxonMobil Chemical Patents Inc
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2601/14—The ring being saturated

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Abstract

This invention relates to the production of terephthalic acid by 1) cycloaddition of 2,5 substituted furan (such as 2,5-bis hydroxymethylfuran or 5 -hydroxy methylfurfural) and ethylene, and 2) the subsequent oxidation of the dehydrated cycloaddition product to terephthalic acid. The invention relates more particularly to overall biobased pathways for making terephthalic acid from carbohydrates such as hexoses (e.g., glucose or fructose).

Description

The preparation method of p-phthalic acid
Inventor: GuangCao, JamesR.Lattner, JavierGuzman, ShifangL.Luo, GaryD.Mohr
Priority
This application claims the USSN61/898 submitted on November 1st, 2013, the priority of 521, the disclosure of described document is incorporated herein by reference in full. The application also requires the priority of the EP14153048.5 in submission on January 29th, 2014.
Technical field
The present invention relates to by the furan replaced and ethylene making p-phthalic acid. The present invention more particularly relates to be prepared the overall biological base path of p-phthalic acid by carbohydrate such as hexose (such as, glucose or fructose).
Background technology
P-phthalic acid can be used for preparing various polymer such as poly-(ethylene glycol terephthalate), poly-(propylene glycol ester terephthalate) and poly-(mutual-phenenyl two acid bromide two alcohol ester). Terephthalate polymer, for instance poly-(ethylene glycol terephthalate) (PET) has many application, for instance, it is used for manufacturing synthetic fibers and food-grade container (such as, carafe). The main source of p-phthalic acid includes aoxidizing the xylol stream deriving from crude oil refine. The growing concern relevant to the high cost preparing hydrocarbon fuel components and petroleum chemicals such as xylol causes the attention substituting such as renewable raw materials of originating. Renewable biomass resource can be used for the substitute of the derivative product of synthetic petroleum and the method being constantly needed to from organism-based raw material synthesis the additional compound being oil and/or petrochemical products traditionally. But, the difficulty that the carbohydrate of natural 6-carbon builds section such as glucose or the desirable final products of fructose converting one-tenth has been hindered the progress in some key areas. Up-to-date research has shown that the feasibility of carbohydrate-modifying for hexose one-tenth 2,5-dimethyl furan (DMF). Such as, Leshkov, etc. Y.R. report and prepare 5 hydroxymethyl furfural (HMF) with high yield as follows: by levulinic acid catalytic dehydration, it is then used by the catalyst based on copper and HMF selective hydration is become DMF (NATURE, in June, 2007, (447): pp.982-5). Additionally, Zhao, H. etc. describe begins at l-alkyl-3-methylimidazolium chloride from glucoseIn metal halide (such as, Chlorizate chromium (II)) exist lower synthesis HMF (Science, in June, 2007, (Vol.316, No.5831); Pp.1597-1600).
US7,385,081 describes and is synthesized p-phthalic acid by carbohydrate derivates. First HMF is oxidized to furan dicarboxylic acid (FDCA), then can be esterified into 2,5-furan dicarboxylic acid esters. Make ethylene and described FDCA or dicarboxylic ester react to form two cyclic ethers, then make described two cyclic ethers be dehydrated into p-phthalic acid or terephthalate. This is called route I.
Route I
WO2010/151346 discloses by making DMF and ethylene when cycloaddition reaction and xylol is prepared in reaction in the presence of a catalyst. Then the p xylene oxidation prepared by this route can be become p-phthalic acid. This is called route II.
Route II
AmericanChemicalSocietyCatalysis2012,2, pp.935-939 disclose HMF are changed into dimethyl furan, then pass through cycloaddition and described dimethyl furan is changed into xylol.
Other list of references of interest includes: US6,245,920, WO2012/125218, WO2013/040514 and WO2013/048248.
The method being prepared p-phthalic acid and terephthalate by the parent material of some biomass derived is mentioned in WO2010/148081 and WO2010/151346.
Low-yield (according to US7,385,081, less than 1%) is locked in carbohydrate-modifying one-tenth p-phthalic acid or ester (being formed the dimethyl ester of FDCA or FDCA) in ethylene cycloaddition step via route I. Via route II, carbohydrate-modifying one-tenth xylol is locked into the hydrogen that every a part HMF needs to add 3 molecules in order to prepare DMF. The hydrogen of this interpolation eventually serves as the water being finally oxidized in the step of p-phthalic acid and removes. It is desirable that the route from carbohydrate to p-phthalic acid does not lock into low-yield (route I) or adds the needs of many mol of hydrogen (route II) for each carbohydrate molecule. What is also needed is the improvement to route II, be wherein compared to, with xylol, the intermediate molecule being oxidized to p-phthalic acid more activity by generation mutually and promote last oxidation step.
Summary of the invention
Summary of the invention
The present invention relates to use diels-Alder (DielsAdler) cycloaddition reaction ethylene and furan (SF) converting compounds replaced is become p-phthalic acid, especially by 5 hydroxymethyl furfural (HMF) or 2, the double; two hydroxymethylfurans (BHMF) of 5-changes into two cyclic ethers, then described two cyclic ethers are dehydrated into 2,5 phenyl replaced, then the phenyl that described 2,5 replace is oxidized to p-phthalic acid. Advantageously, this path does not require to be hydrogenated by described SF before ethylene cycloaddition step.
In the first embodiment, the present invention relates in ethylene cycloaddition to the furan of the replacement represented by below formula:
With the bicyclic compound that preparation is represented by below formula:
Then by described bicyclic compound dehydration to form the phenyl replaced, below formula represent:
Wherein R is=O, OH, OC (O) CH3 and R*It is=O, OH, OC (O) CH3 or H, then can be oxidized into p-phthalic acid. In a preferred embodiment in accordance with this invention, described SF was not hydrogenated to dialkyl group (such as, R and R before described cycloaddition step*It is not all alkyl). But, in some embodiments of the present invention, SF can before described cycloaddition step partial hydrogenation. Such as, HMF can become BHMF by partial hydrogenation before described cycloaddition step, but is not exclusively hydrogenated to 2,5-dimethyl furans. Or, added less than bimolecular hydrogen for each SF molecule before ethylene cycloaddition step.
As follows, the cycloaddition of ethylene obtains intermediate two cyclic ether compounds, subsequently described intermediate two cyclic ether compounds is dehydrated into Isosorbide-5-Nitrae-dibasic benzyl ring. Then the dibasic phenyl of described 1,4-can be oxidized to p-phthalic acid:
In one embodiment of the invention, ethylene is made to react with HMF when first not adding hydrogenation gas.Ethylene cycloaddition and HMF dehydration subsequently produce 4-(methylol) benzaldehyde (HMBA), as follows, are called route III:
Route III
In another embodiment of the invention, first with a part hydrogen, the hydrogenation of HMF molecule is obtained BHMF. The ethylene cycloaddition of BHMF and dehydration obtain Isosorbide-5-Nitrae-phenylene dimethanol (PDM), as follows, are called route IV:
Route IV
Described 1,4-phenylene dimethanol (PDM) can be oxidized to p-phthalic acid subsequently. Or, PDM may be used for other application, for instance, form diester by adding organic acid, or prepare polyester by being polymerized with diacid.
In any one in route III or IV, it is more active that xylol intermediate phase comparison prepared by the product of cycloaddition and dehydration and pass course II is oxidized to p-phthalic acid. This is because when being prepared by route III or IV respectively, the substituent group (such as methyl) on the phenyl ring in HMBA or PDM intermediate is already partially oxidised.
Accompanying drawing is sketched
Fig. 1 illustrates the present invention preferred embodiment according to route III.
Fig. 2 illustrates the present invention preferred embodiment according to route IV.
Fig. 3 illustrates the preferred embodiment of route III, and wherein identical solvent extracts and cycloaddition/dehydration for HMF.
Fig. 4 illustrates the preferred embodiment of route III, and wherein HMBA is used as the solvent in HMF extraction and ethylene cycloaddition/both dehydrations.
Fig. 5 illustrates the preferred embodiment of route IV, and wherein identical solvent extracts for HMF, HMF hydrogenates and cycloaddition/dehydration.
Fig. 6 illustrates the preferred embodiment of route IV, and wherein PDM is used as the solvent in HMF extraction, HMF hydrogenation and ethylene cycloaddition/dehydration.
Fig. 7 illustrates the preferred embodiment of the cycloaddition/dehydration of arbitrary route III or IV.
Detailed Description Of The Invention
The new numbering plan of each race of the periodic table of elements used herein according to ChemicalandEngineeringNews, 63 (5), p.27, described in (1985).
Term " replacement " refers to that hydrogen-based is replaced with alkyl, hetero atom or containing heteroatomic group. Such as, 2,5-dimethyl furans are the furyls having methyl 2 and 5 replacements.
Term " alkyl (hydrocarbylradical) ", " alkyl (hydrocarbyl) " and " alkyl (hydrocarbylgroup) " is used interchangeably in whole file. For present disclosure, " alkyl " is defined as C1-C20Group, they can be linear, branching or ring-type (aromatics or non-aromatic), for instance methyl, ethyl, vinyl; Isomer with propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl and/or dodecyl. The example that " alpha-olefin " is the alkene and alpha-olefin that have double bond in α (or 1-) position includes ethylene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-endecatylene and 1-dodecylene.
5 hydroxymethyl furfural (HMF) is represented by below formula:
The double; two hydroxymethylfurans (BHMF) of 2,5-is represented by below formula:
BHMF can pass through to obtain 5 hydroxymethyl furfural hydrogenation, and such as " CatalyticHydrogenationoverPlatinumMetals ", P.N.Rylander, AcademicPress, disclosed in NewYork, 1967, pp.246-249.
Hereinafter referred to as using in entire disclosure: Me is methyl, and Ph is phenyl, and RT is room temperature, unless otherwise prescribed, it is stipulated that being 25 DEG C, tol is toluene.
The present invention is relevant with the method that the furan (SF) replaced changes into two cyclic ethers, then described two cyclic ethers dehydrations is formed the phenyl replaced, then the phenyl of described replacement is oxidized to p-phthalic acid. Preferably, added less than bimolecular hydrogen (being preferably less than 1.5 molecules, it is preferable that less than 1 molecule, it is preferable that SF is not hydrogenated) for each SF molecule before changing into two cyclic ethers. Or, before changing into two cyclic ethers, add the hydrogen less than two moles for each mole of SF, it is preferable that less than 1.5 moles, it is preferable that less than 1 mole, it is preferable that SF is not hydrogenated. More specifically, ethylene is to SF, for instance the cycloaddition of BHMF or HMF, the dehydration of two cyclic ethers then formed, then aoxidize, it is possible to for preparing p-phthalic acid with good productivity and production cost saving, because reduce or eliminating the step of hydrogenation (one or more) of costliness. In an optional embodiment, by BHMF and acid, for instance acetic acid combines, to prepare diester before cycloaddition.
In a preferred embodiment, the preparation method that the present invention relates to p-phthalic acid, including make the furan of replacement and ethylene when cycloaddition reaction and in the presence of catalyst (such as the activated carbon of activated carbon, pickling, silicon dioxide, aluminium oxide, zeolite molecular sieve or non-zeolite molecular sieve) reaction to prepare two cyclic ethers, then described two cyclic ethers dehydrations are formed the phenyl replaced, afterwards, the phenyl of described replacement is oxidized to p-phthalic acid, and the furan of wherein said replacement is represented by below formula:
Described two cyclic ethers are represented by below formula:
The phenyl of described replacement is represented by below formula:
Wherein R is=O, OH or OC (O) CH3, R*It is=O, OH, OC (O) CH3 or H, but condition is R and the R on described SF*Corresponding alkyl it was not hydrogenated to before described cycloaddition step. Therefore, in a preferred embodiment in accordance with this invention, before ethylene cycloaddition step, the hydrogen less than two moles is added for each SF molecule, it is preferable that less than 1.5 moles, it is preferable that less than 1 mole, it is preferable that do not hydrogenate SF before described cycloaddition step.
In a preferred embodiment in accordance with this invention, the furan of described replacement is represented by below formula:
And/or
Described two cyclic ethers are represented by below formula:
And/or
The phenyl of described replacement is represented by below formula:
Wherein R*It is=O, H or OH, it is preferable that=O or OH.
In a preferred embodiment in accordance with this invention, R and R*Identical. In another embodiment of the invention, R and R*Different. In a preferred embodiment in accordance with this invention, R is OH and R*It is=O. In another embodiment of the invention, R and R*It is OH or R and R*It is all=O.
Advantageously, SF (such as BHMF or the HMF) parent material of described method can be synthesized by carbohydrate, provides the Production of Terephthalic Acid route relying on renewable raw materials at least partly accordingly. Such as, use glucose or fructose as SF, for instance the source of BHMF or HMF obtains the method that in wherein 8 p-phthalic acid carbon atoms, 6 (75%) derives from carbohydrate. Additionally, the ethylene used as the reactant in the method according to the invention is obtained by wood-based composites, then the p-phthalic acid prepared is completely derived from (that is, in its 8 carbon atoms whole 8) renewable raw materials.
The use of solvent can be used for forming HMF from sugar, and can be used for ethylene cycloaddition reaction. Such as, Leshkov, etc. Y.R. report and use biphasic reaction flow process to prepare 5 hydroxymethyl furfural (HMF) with high yield by the acid-catalyzed dehydration of fructose, wherein from water-containing reacting medium solvent extraction HMF product, such as with butanol as solvent (NATURE, in June, 2007, (447): pp.982-5).In ethylene cycloaddition reaction, Chang etc. reports and uses hexane solvent to prepare xylol (GREENCHEMISTRY (2013) DOI:10.1039/c3gc40740c) in the ethylene reaction with DMF. In additional embodiment, HMF production stage uses the solvent identical with ethylene cycloaddition step. When hydrogenating HMF (with less than two mol of hydrogen/mole HMF), identical solvent is used for whole three steps. In another embodiment, the solvent used is ethylene cycloaddition with the identical material of preparation in dehydration such as, the HMBA in route III and the PDM in route IV.
It in cycloaddition/dehydration, reactant mixture exists water and is probably disadvantageous, because can make furan nucleus hydrolysis and/or slows down or limit dehydration. In another embodiment, remove water from reactant mixture continuously as follows: allow Excess ethylene circulate through reacting fluid, make water condense from the ethylene effluent of gaseous state and separate, and unreacted ethylene vapor is sent back to reactant mixture.
The preparation method that embodiment of the present invention relate to p-phthalic acid, including the furan making replacement, such as BHMF or HMF and ethylene are when cycloaddition reaction, preferably react in the presence of a catalyst to prepare two cyclic ethers, then by described two cyclic ethers dehydrations to prepare the phenyl replaced, then the phenyl of described replacement is oxidized to p-phthalic acid. Representational cycloaddition reaction condition includes the temperature of about 100 DEG C (212)-about 300 DEG C (572), about 1000kPa (145psig)-about 10, the ethylene partial pressure of 000kPa (14500psig), and the reactor residence time of about 1 hour-about 48 hours. Described method can interval or carry out in a continuous manner, for instance allow SF, for instance BHMF or HMF and ethylene reaction thing pass through continuously on catalyst fixed bed. Representational catalyst is activated carbon (such as in solidapowder form), especially already by with acid such as H3PO4The carbon washed and be activated. Other solid material, especially has high surface (such as, zeolite or non-zeolite molecular sieve) and/or has those of absorbability for aromatics and olefinic feed component and be also used as catalyst. These catalyst any can optionally promote with alkali metal or alkaline earth promoters.
Cycloaddition reaction condition and catalyst can provide SF, at least about the 50% of such as BHMF or HMF converts, wherein p-phthalic acid accounts at least about the 60% of the furan of conversion, mole (namely based on, for at least about 60% selectivity of p-phthalic acid, or prepared by least about 0.6 moles terephthalic acid for each mole of SF converted).
Therefore, according to an embodiment of the present invention, hexose such as glucose or fructose is to SF, for instance HMF or BHMF converts, then cycloaddition, is then oxidized to p-phthalic acid and provides the basis using at least one renewable carbohydrate raw material to prepare p-phthalic acid. The embodiment that the present invention is particularly useful relates to the method based on carbohydrate preparing p-phthalic acid, including by hexose such as glucose or fructose converting one-tenth HMF or BHMF, then the phenyl replaced with ethylene cycloaddition preparation, is then oxidized to p-phthalic acid by the phenyl of described replacement.
Without wishing to being subject to theoretical constraint, it is believed that reaction carries out to the diels of the furan nucleus of HMF or BHMF-Alder cycloaddition via ethylene, and then open loop produces dibasic phenyl with dewater (dehydration).The catalyst and the reaction condition that are suitable for can improve productivity ratio or productivity, particularly compared with heat or uncatalyzed reaction. Term " catalyst " and " catalysis " are intended to reduce the reagent of the activation energy required for desired reaction, and improve the accelerator of the effectiveness of this type of reagent.
The catalyst being suitable for includes the carbon with high surface, especially activated carbon, for instance have at least about 700 meters squared per gram (m measured according to BET method (ASTM6556-09)2/ gram) surface area. It is said that in general, surface area is at the about 3000m of about 700-2/ gram, the about 1500m of generally about 700-2/ gram scope in. There is the catalyst of special advantage and include with acid, for instance, phosphoric acid washing and the carbon that is activated, to provide high surface in these representational scopes and other desirable performances many possibly. These performances include the total oxygen content of at least about 1wt% (such as, the about 20wt% of about 1wt%-, the about 10wt% of generally about 1wt%-).
Hot-working or activation may also be used for obtaining the porous carbon granule with big internal surface area. No matter activate whether chemically or carry out with hot mode, activated carbon granule can granular, spherical, pellet or powder, supplied by many commercial manufacturers, including NoritAmericas, Inc. (Marshall, TXUSA), JapanEnviroChemicals (Tokyo, Japan), JacobiCarbonsAB (Kalmar, and CalgonCarbonCorporation (Pittsburg, PA) Sweden). For the representational particle mean size of Powdered Activated Carbon of method described herein less than about 300 microns (50 orders) and generally in the scope of about 50 microns (300 orders)-about 300 microns (50 orders). Screening can be used in some cases to reach desired particle mean size.
It is said that in general, activated carbon is derived from organic origin, for instance timber, grind Exocarpium cocois (Cocos nucifera L) etc. Various forms of activated carbons include the activated carbon of surface oxidation, graphite, graphite oxide or carbon nanomaterial. Carbon nanomaterial includes, but are not limited to CNT, carbon nanohorn, carbon nano-fiber, buckyball (buckyball) etc. Absorbent charcoal material also includes having those of one or more surface modifications, such as, be carried out as follows surface modification: covalency keyed jointing is acid or basic matterial with Controlled acidity and/or introduce one or more for absorption organic compound convert the metal of activity in catalysis. Therefore these surface modifications can supplement the catalysis activity that (promotion) activated carbon converts for expectation.
Except activated carbon, there is higher BET surface area { such as, at least about 200m2/ gram, generally about 200m2/ gram-about 500m2/ gram), and other materials many with enough absorbed organic reactant abilities are also used as solid catalyst. These materials include inorganic oxide such as silicon dioxide (such as, in silica gel form), aluminium oxide, zirconium oxide etc., and zeolite molecular sieve and non-zeolite molecular sieve. The zeolite molecular sieve being suitable as catalyst is crystal aluminosilicate, and it is calcination form, it is possible to expressed by the following formula:
M2/nO:Al2O3:xSiO2:yH2O
Wherein M is cation, for instance H, alkali metal (Na, K etc.), alkaline-earth metal (Mg, Ca etc.), rare earth metal (La, Y etc.) and transition metal, and NH4, n is cationic quantivalence, and x has the value of about 5-100, and y has the value of about 2-10. Zeolite and has been described in detail in other place at ZeoliteMolecularSieves, JohnWileyandSons, NewYork (1974) by D.W.Breck.In useful embodiment, catalyst includes large pore zeolite, for instance Y, zeolite beta, modenite, ZSM-12, ZSM-18, MCM-22 and/or MCM-49 and/or mesopore zeolite, for instance ZSM-5, ZSM-11, ZSM-23, ZSM-48 and ZSM-57.
In useful embodiment, catalyst includes zeolite, such as ZSM-5, zeolite beta, ITQ-13, MCM-22, MCM-49, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-48, ZSM-57, preferably modified so that working as at the temperature of 120 DEG C and when measuring under 2,2-dimethylbutane pressure of 60 holders (8kPa), there is about 0.1-15Sec already by decatize-1The diffusion parameter to 2,2-dimethylbutane. Or, catalyst can include ZSM-5, MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, ITQ-13, ITQ-39, MCM-36, MCM-49, MCM-56, X zeolite, zeolite Y, zeolite beta etc. Diffusion parameter is defined in [0033] section of WO2013/009399.
Non-zeolite molecular sieve includes the molecular sieve based on anhydrous basis with the chemical composition represented by following empirical formula:
(ELxAlyPz)q2
Wherein EL is chosen from the element of silicon, magnesium, zinc, ferrum, cobalt, nickel, manganese, chromium and its mixture, x is the molar fraction of EL and is at least 0.005, and y is the molar fraction of Al and is at least 0.01, and z is the molar fraction of P and is at least 0.01, x+y+z=l, q are oxygen. When el is a mixture of metals, x represents the total amount of the element mixture existed. Preferred element (EL) is silicon, magnesium and cobalt, and wherein silicon is particularly preferred. These non-zeolite molecular sieves are also referred to as " ELAPO ". Various ELAPO are prepared by as known in the art and describe such as, in US7,317,133, US5,191,141, US4,554,143, US4,440,871, US4,853,197, US4,793,984, US4,752,651 and US4,310,440.
As noted before, any of above solid catalyst can include the metallic promoter agent that desired conversion has catalysis activity. Representational metal includes alkali and alkaline earth metal ions, and rare earth and transition metal. The combination of two or more metals can use (such as, as carrier material) with the combination of any of the above described solid catalyst.
Or, any catalyst disclosed in ACSCatalysis, 2012,2, pp.935-939 can use at this.
The reaction of HMF and/or BHMF and ethylene carries out when applicable cycloaddition reaction under above-mentioned catalyst exists. It can be advantageous to make the use being not involved in the solvent (such as, dimethyl sulfoxide) of desired response path minimize or even get rid of. According to some embodiments, therefore, cycloaddition reaction condition includes solvent-free or substantially solvent-free reactant mixture (that is, containing less than about 10%, less than about 5%, or the solvent even less than about 1%). Wherein arrange the reactor of catalyst or reaction zone (such as, fixing or the moving bed being arranged in batch reactor or be arranged as in continuous reaction system) in exemplary temperature in about 100 DEG C (212)-about 300 DEG C (572), in the scope of generally about 150 DEG C (302)-about 225 DEG C (437). Favourable cycloalkylation reaction condition also includes at least about 1000kPa (145psig), general about 1000kPa (145psig)-about 10, the ethylene partial pressure of the about 5000kPa of 000kPa (1450psig), generally about 2000kPa-.Gross pressure generally exceeds about 2%-about 50% than ethylene partial pressure, this is owing to (i) SF (i.e. HMF and/or BHMF) vapour pressure at the reaction temperatures, and/or (ii) possible diluent and/or the impurity (such as, the ethane) contribution to the gross pressure in reactor or reaction zone.
No matter whether reaction intermittently or continuously carries out, cycloaddition reaction condition is also commonly included in about 1 hour-about 48 hours, the reactor residence time in the scope of generally about 3 hours-about 30 hours. But, wherein by unconverted SF and/or ethylene recycle to provide the continuation method of higher overall conversion when, reactor residence time can significantly decrease, even if one way (per-pass) conversion ratio is also significantly less such. Reactant SF can be continuously fed cycloaddition reaction district, for instance, by the liquid hourly space velocity (LHSV) (LHSV) of the about 5hr of about 0.05hr-. As is understood in the art, liquid hourly space velocity (LHSV) (LHSV represents with unit hr) is the equivalents divided by bed volume the catalyst bed volume representing the liquid processed per hour of the volume of liquid flow velocity above catalyst bed. LHSV is therefore closely related with the inverse of reactor residence time.
Be all electron-donating group if instead of base, then diels-Alder the cycloaddition of 2,5-dibasic furan will be promoted by ethylene. In 5 hydroxymethyl furfural, one of substituent group is formaldehyde, and it is electrophilic, and another is the methylol of supplied for electronic. The selectivity addition of the carboxaldehyde radicals on HMF molecule will be made electrophilic carbonyl change into supplied for electronic methylol by one hydrogen molecule. The double; two hydroxymethylfurans (BHMF) of the 2,5-of gained has more reactivity as dienophile with in adopting BHMF or HMF as the diels-Alder cycloaddition reaction of diene than 5 hydroxymethyl furfural (HMF) adopting ethylene. The selective hydration of furan-2-formaldehyde (or furfural) becomes 2-furancarbinol (or furfuryl alcohol) to be known to the skilled in furfuryl alcohol production field. The early stage works of Kaufmann and Adams reports on the platinum catalyst of reduction furfural to the high conversion of furfuryl alcohol and selectivity (J.Am.Chem.Soc., Dec1923, pp.3029-3044). There was reported the conversion on nickel and palladium catalyst. In the newer works of Sharma et al., report furfural on Cu:Zn:Cr:Zr catalyst to convert to the 100% of furfuryl alcohol, there is the selectivity (App.CatA:Gen454, pp.127-136 (2013) DOI:10.1016/j.apcata.2012.12.010) of 96%. Similar catalyst and condition can be used to 5 hydroxymethyl furfural changes into the double; two hydroxymethylfurans of 2,5-.
In exemplary continuation method, reactant SF and ethylene are continuously fed one or more reactors of fixing bed containing catalyst (such as, in oscillating bed (swing-bed) reactor assembly with multiple fixed bed reactors), and the product of the Isosorbide-5-Nitrae-dibasic phenyl (such as HMBA or PDM) being continuously taken out comprising conversion is together with unconverted reactant and byproduct of reaction. The unconverted material of preferable separate, for instance, the relative volatility difference based on them uses one or more lock out operation (such as, flash separation or distillation) to adopt single phase or the contact of multistage vapor-liquid equilibrium to be easily separated.
According to a particular, single phase flash separation is used to separate unconverted ethylene from cycloaddition reaction district effluent, together with lower boiling by-product and impurity. Then allow the liquid bottoms product stream of this flash separation at least one multistage distillation column with the dibasic phenyl of the 1,4-reclaiming purification individually and unconverted SF.Can by unconverted SF and/or unconverted ethylene recycle to cycloaddition reaction district, after optionally in purging these streams, the part of any one or both has the gathering of the by-product of similar boiling points with restriction. In a specific embodiment, Excess ethylene is added in reactor with from reaction zone water stripping; Make this water-cooled coalescence and ethylene separation, be then recycled to reactor. According to a specific continuous operation, control ethylene reaction thing to the flow velocity of cycloaddition reaction device or reaction zone to maintain desired gross pressure. Based on the operation of pressure requirements, this kind guarantees that ethylene is by substantially consuming the speed supply matched plus loss (causing owing to dissolving and gas purging (aerofluxus) possibly) with it.
Whether use intermittently or serially method that SF is catalytically converted into the phenyl of replacement, cycloaddition reaction condition generally provides at least about 50%, such as about 50%-about 90%, the SF conversion ratio (this can be the conversion per pass in cycloaddition reaction district, when being operated with the circulation of unconverted SF) of generally about 50%-about 75%. The circulation of unconverted SF, for instance circulation is to disappearing or almost disappearing, it is provided that overall conversion completely or almost completely. In the SF converted, the selectivity of the phenyl replaced is usually at least about 60%, refers to and at least about 0.6 mole of phenyl replaced is produced for each mole of SF converted. Typical selectivity to the phenyl replaced is about 60%-about 95%. In view of these representational conversion ratio and selective value, the gross production rate of the phenyl replaced is usually at least about the 30% of theoretical yield, generally about 30%-about 90%, generally about 90%-about 75%, described theoretical yield is based on the conversion completely to the phenyl replaced of SF and stoichiometry (1:1 mole) ethylene and does not have by-product to be formed.
After being combined with ethylene and add catalyst by SF, form two cyclic ethers. Then preferably described ether dehydration is formed the phenyl of replacement. Described bicyclic compound in same reaction step and under same catalyst exists, and can experience dehydration identical with ethylene cycloaddition reaction when.
After being combined with ethylene and add catalyst by SF, form two cyclic ethers. Then preferably described ether dehydration is formed the phenyl of replacement, then the phenyl of described replacement is oxidized to p-phthalic acid. Can use for p xylene oxidation becomes the same procedure of p-phthalic acid the phenyl of described replacement is oxidized to p-phthalic acid. Expection, relative to the methyl substituents in xylol, carbonyl or methylol on benzyl ring replace generation oxidation reaction and will be more prone to. Expection, the reactivity being more prone to of carbonyl or hydroxymethyl substituents is converted into the higher selectivity to p-phthalic acid.
Or, the phenyl of replacement can use and the different Catalyst And Method of the commercial oxidation practice for xylol to the oxidation of p-phthalic acid. These methods will utilize the advantage that methylol and aldehyde radical compared with the methyl of xylol are higher to the reactivity of oxidation. Many catalyst systems are known is high activity and selective for primary alconol to the conversion of carboxylic acid. Such as, Gorbanev etc. describe at Ru (OH) x/CeO2On catalyst in water-bearing media ethanol to the Quantitative yield of acetic acid. Other effective catalyst includes Mo, V, NB and the mixed oxide of Pd (ACSCatalysis (2012) 2,604-612, DOI:10.1021/cs200554h).
P-phthalic acid may be used in method well known in the art and prepares polyester such as polyethylene terephthalate polymer (PET). Once manufacture, it is possible to processing PET is so that preparation is for synthetic fibers, beverage, food and other liquid container; Thermoforming is applied; Thermoplastic PET resin with the engineering resin being generally combined with glass fibre.
Turning now to accompanying drawing, Fig. 1 illustrates the present invention preferred embodiment according to route III. First by raw material (100), preferred renewable raw materials, such as sugar, cellulose or lignocellulose change into 2,5-dibasic furan compound (200) such as 5 hydroxymethyl furfurals (HMF) (300), release water (250). Then described HMF is allowed to experience cycloaddition condition (400) with ethylene (500) and form two cyclic ethers intermediate, subsequently by described two cyclic ethers intermediate dehydration (600), release water (250) becomes Isosorbide-5-Nitrae-dibasic phenyl such as 4-(methylol) benzaldehyde (HMBA) (700). Optionally in the presence of oxygen (850), this product can be aoxidized (800) and become p-phthalic acid (900).
Fig. 2 illustrates the present invention preferred embodiment according to route IV. First by raw material (100), it is preferable that renewable raw materials, for instance sugar, cellulose or lignocellulose change into 2,5-dibasic furan compound (200) such as 5 hydroxymethyl furfurals (HMF) (300). Then in the presence of hydrogen (280), with less than two mol of hydrogen, described HMF is hydrogenated (275) with for each mole of furan, and form the double; two hydroxymethylfurans (BHMF) (290) of partially hydrogenated furan compound such as 2,5-. Then described partially hydrogenated furan ethylene (500) experience cycloaddition 400 condition is allowed to form two cyclic ethers intermediate, subsequently described two cyclic ethers intermediate dehydration (600) are become 1, the dibasic phenyl of 4-such as Isosorbide-5-Nitrae-phenylene dimethanol (PDM) (650). Optionally in the presence of oxygen (850), this product can be aoxidized (800) and become p-phthalic acid (900).
Fig. 3 illustrates the preferred embodiment of route III, and wherein identical solvent extracts and cycloaddition/dehydration for HMF. In the first step, as by Leshkov, Y.R. etc. what describe uses two-phase reactor (950) like that, there is organic facies (950A) and aqueous phase (950B) by raw material (100), it is preferably derived from biomass, acid catalyst (855) is generally used to change into HMF (300) and HMF is extracted into (NATURE in organic solvent (955) such as butanol, methyl iso-butyl ketone (MIBK), toluene or their mixture, in June, 2007, (447) pp.982-5). HMF (300) and ethylene (500) is made to react in the second step of (400) wherein, regardless of exsolution agent and as the solvent in ethylene cycloaddition step. Then solvent is separated and is recycled to first step (980) with product (975). Additional solvent solvent as a supplement (990) can be added. Dead catalyst (951) and moisture by-product (952) can be intermittently or continuously removed from two-phase reactor (950).
Fig. 4 illustrates the preferred embodiment of route III, and wherein HMBA is used as the solvent in HMF extraction and ethylene cycloaddition/both dehydrations. Step is identical with Fig. 3, but wherein avoids from HMBA product separation solvent.
Fig. 5 illustrates the preferred embodiment of route IV, and wherein identical solvent extracts for HMF, HMF hydrogenates and cycloaddition/dehydration. In the first step, as by Leshkov, Y.R. etc. what describe uses two-phase reactor (950) like that, there is organic facies (950A) and aqueous phase (950B) by raw material (100), it is preferably derived from biomass, acid catalyst (855) is generally used to change into HMF (300) and HMF is extracted into (NATURE in organic solvent (955) such as butanol, methyl iso-butyl ketone (MIBK), toluene or their mixture, in June, 2007, (447) pp.982-5).Regardless of exsolution agent before second step, wherein in same solvent, form BHMF (290) and water (250) for each mole of HMF with HMF being hydrogenated (275) less than two mol of hydrogen (280). HMF and ethylene (500) is made to react in the third step of (400) dehydration (600) wherein, regardless of exsolution agent and as the solvent in ethylene cycloaddition step. Then solvent (955) is separated with product PDM (650) (975) and circulates (980) to first step. Additional solvent solvent as a supplement (990) can be added. Dead catalyst (951) and moisture by-product (952) can be intermittently or continuously removed from two-phase reactor (950).
Fig. 6 illustrates the preferred embodiment of route IV, and wherein PDM is used as the solvent in HMF extraction, HMF hydrogenation and ethylene cycloaddition/dehydration. Step is identical with Fig. 5, but wherein avoids from PDM product separation solvent.
Fig. 7 illustrates the preferred embodiment of the cycloaddition/dehydration of arbitrary route III or IV. Raw material HMF (300) or BHMF (290) is supplied cycloaddition/dehydration reactor (401) plus non-essential solvent (955), described reactor has gas phase (401A) and aqueous phase (401B), and containing catalyst (420). Ethylene (500) is added in described reactions steps, wherein removes Excess ethylene from the gas phase of described reactor. Excess steam is used for from liquid reaction mixture water stripping. Vapor effluent stream (512) is cooled down (283), wherein also from reactor condensate water stripping and some organic materials. Water (250) is separated (430) with unreacted ethylene vapor (431A) and any organic facies (256), and discharges from system. Via compressor (502), ethylene vapor (501) is sent back to reactor. Can using any condensation organic facies reclaimed in separator or send back to reactor (257A) or as product (257B) discharge. Liquid product (407) is removed from reactor (401).
R and R in another embodiment of the invention, on the phenyl replaced*During containing OH base, it is possible to the phenyl of described replacement is hydrogenated to the monomer that cycloalkane is not necessarily used as in production of polyester.
Such as:
There is no the ring filling of the hydrogenolysis of methylol, for instance Isosorbide-5-Nitrae-benzene dimethanol is hydrogenated to 1,4-CHDM requirement catalysts selective (such as base metal catalysts Ni, Cu or noble metal Rh, Pt or many metallized metals catalyst). Typical condition includes the Hydrogen Vapor Pressure of 100-5000kPag and the temperature of 0 DEG C-200 DEG C.
Both above glycol molecules can be used as to prepare the comonomer of polyester independently or together. Especially, 1,4-CHDM is one of most important comonomer for preparing polyethylene terephthalate (PET). Currently, 1,4-CHDM is prepared via the hydrogenation at high temperature and pressure of terephthalate such as dimethyl terephthalate (DMT).
In another embodiment, the glycol (aromatics or non-aromatic) prepared here can esterified and be used as polar polymer (such as polrvinyl chloride and PET) plasticizer. For example, it is possible to by Isosorbide-5-Nitrae-benzene dimethanol and/or 1,4-CHDM and 2 moles of RCOOH, (wherein R is C1-C20Alkyl) and catalyst (such as sulphuric acid) combine to obtain diester (as follows).
This type of diester can be used as plasticizer, especially the plasticizer of polrvinyl chloride and pet polymer.
Polar polymer is by the polymer manufactured containing heteroatomic monomer.
The present invention relates in another embodiment:
1. the preparation method of p-phthalic acid, and with ethylene react in the presence of a catalyst when cycloaddition reaction and prepare two cyclic ethers including the furan making replacement, the phenyl of replacement is prepared by described two cyclic ethers dehydrations, afterwards the phenyl of described replacement being oxidized to p-phthalic acid, the furan of wherein said replacement is represented by below formula:
Described two cyclic ethers are represented by below formula:
The phenyl of described replacement is represented by below formula:
Wherein R is=O, OH, OC (O) CH3, R*It is=O, OH, OC (O) CH3 or H,
But condition is two substituent groups on described SF was not hydrogenated to corresponding alkyl before described cycloaddition step.
2. the method for section 1, wherein said cycloaddition reaction condition includes the temperature of about 100 DEG C-about 300 DEG C.
3. the method for sections 1 or 2, wherein said catalyst includes activated carbon, silicon dioxide, aluminium oxide, zeolite molecular sieve or non-zeolite molecular sieve.
4. the method for sections 3, wherein said catalyst includes activated carbon.
5. the method for sections 4, wherein said activated carbon is pickling.
6. the method for either segment in section 1-5, at least 6 in the carbon atom of wherein said p-phthalic acid are derived from one or more raw materials that can regenerate every year.
7. the method for either segment in section 1-6, the furan of wherein said replacement is obtained by the conversion of glucose or fructose.
8. the method for either segment in above-mentioned section of 1-7, the furan of wherein said replacement includes 5 hydroxymethyl furfural.
9. the method for either segment in above-mentioned section of 1-8, the furan of wherein said replacement includes 2,5-double; two hydroxymethylfurans.
10. the method for section 7, the furan of wherein said replacement is obtained by glucose or fructose converting one-tenth 5 hydroxymethyl furfural.
11. the method for section 10, wherein said 5 hydroxymethyl furfural with ethylene cycloaddition before be not converted into 2,5-dimethyl furans.
12. prepare the method based on carbohydrate of p-phthalic acid, including:
A hexose is changed into 5 hydroxymethyl furfural by ();
B () makes described 5 hydroxymethyl furfural and ethylene when cycloaddition reaction and react in the presence of a catalyst and prepare two cyclic ethers, then make the compound that described two cyclic ethers dehydrations and preparing are represented by formula (I):
With
C the compound oxidation represented by formula (I) is prepared p-phthalic acid with oxygen by (); Wherein said 5 hydroxymethyl furfural was not converted into 2,5-dimethyl furan before step (b).
13. prepare the method based on carbohydrate of p-phthalic acid, including:
A hexose is changed into the double; two hydroxymethylfurans of 2,5-by ();
B () makes described 2,5-double; two hydroxymethylfurans when cycloaddition reaction with ethylene and react in the presence of a catalyst and prepare two cyclic ethers, then make the compound that described two cyclic ethers dehydrations and preparing are represented by formula (II):
With
C the compound oxidation represented by formula (II) is prepared p-phthalic acid with oxygen by (); The double; two hydroxymethylfurans of wherein said 2,5-was not converted into 2,5-dimethyl furan before step (b).
14. the method for section 1, the furan of wherein said replacement is represented by below formula:
With
Described two cyclic ethers are represented by below formula:
With
The phenyl of described replacement is represented by below formula:
Wherein R*It is-C=O or-OH.
15. the method for either segment in above-mentioned section of 1-14, the furan of wherein said replacement includes 2,5-double; two hydroxymethylfurans, and described 2,5-double; two hydroxymethylfurans is combined with acid to prepare diester before described cycloaddition step.
16. the method for section 15, wherein said acid is acetic acid.
17. the method for section 1, wherein before described cycloaddition step, add the hydrogen less than 1.5 moles for each SF molecule.
18. the method for section 1, wherein before described cycloaddition step, add the hydrogen less than 1 mole for each SF molecule.
19. the method preparing 1,4-CHDM, including:
A hexose is changed into the double; two hydroxymethylfurans of 2,5-by ();
B () makes described 2,5-double; two hydroxymethylfurans when cycloaddition reaction with ethylene and react in the presence of a catalyst and prepare two cyclic ethers, then make the compound that described two cyclic ethers dehydrations and preparing are represented by formula (II):
With
C the hydrogenation of compounds represented by formula (II) is prepared 1,4 cyclohexane dimethanol with hydrogen by () under existing as Ni, Cu of base metal catalysts or noble metal Rh, Pt or many metallized metals catalyst;The double; two hydroxymethylfurans of wherein said 2,5-was not converted into 2,5-dimethyl furan before step (b).
20. method, including:
A hexose is changed into the double; two hydroxymethylfurans of 2,5-by ();
B () makes described 2,5-double; two hydroxymethylfurans when cycloaddition reaction with ethylene and react in the presence of a catalyst and prepare two cyclic ethers, then make the compound that described two cyclic ethers dehydrations and preparing are represented by formula (II):
With
The double; two hydroxymethylfurans of wherein said 2,5-was not converted into 2,5-dimethyl furan before step (b).
21. the method preparing plastification composite, be combined with one or more diester compounds represented by below formula including by polar polymer:
Wherein R is C1-C20Alkyl.
22. the method for section 21, wherein said polymer includes polrvinyl chloride and/or pet polymer.
23. the method for section 21, wherein said diester compound is derived from Isosorbide-5-Nitrae-benzene dimethanol and/or 1,4-CHDM, and described Isosorbide-5-Nitrae-benzene dimethanol is obtained as below:
A hexose is changed into the double; two hydroxymethylfurans of 2,5-by ();
B () makes described 2,5-double; two hydroxymethylfurans when cycloaddition reaction with ethylene and react in the presence of a catalyst and prepare two cyclic ethers, then make the compound that described two cyclic ethers dehydrations and preparing are represented by formula (II):
Or 1,4 cyclohexane dimethanol is obtained as below: with hydrogen, the compound represented by formula (II) is hydrogenated further under base metal or noble metal (single or multiple metal) catalyst exist and prepare 1,4 cyclohexane dimethanol; The double; two hydroxymethylfurans of wherein said 2,5-was not converted into 2,5-dimethyl furan before step (b).
24. the preparation method of p-phthalic acid, including:
1) hexose changes into the furan of replacement in two-phase reactor, and described reactor has organic facies and aqueous phase;
2) organic solvent is used to extract the furan of described replacement from the material produced by described two-phase reactor;
3) in the combination transfer of solvent and the furan of replacement to cycloaddition reaction device, the furan of described replacement and ethylene wherein will be made under described solvent exists when cycloaddition reaction and to react in the presence of a catalyst and prepare two cyclic ethers,
4), after, described two cyclic ethers dehydrations are produced the phenyl replaced under described solvent exists;
5) reclaim described solvent and described solvent is recycled to step 2; With
6) after, the phenyl of described replacement being oxidized to p-phthalic acid, the furan of wherein said replacement is represented by below formula:
Described two cyclic ethers are represented by below formula:
The phenyl of described replacement is represented by below formula:
Wherein R is=O, OH or OC (O) CH3, R*It is=O, OH, OC (O) CH3 or H,
But condition is R and the R on the furan of described replacement*Substituent group was not all hydrogenated to corresponding alkyl before described cycloaddition step.
25. the method for section 24, wherein (methylol) benzaldehyde is used as furan extraction and the solvent in ethylene cycloaddition/both dehydrations of described replacement.
26. the preparation method of p-phthalic acid, including:
1) hexose changes into the furan of replacement in two-phase reactor, and described reactor has organic facies and aqueous phase;
2) organic solvent is used to extract the furan of described replacement from the material produced by described two-phase reactor;
3) under described solvent exists, the furan of described replacement is combined with the relative each mole of furan the replaced hydrogen less than 2 moles to be hydrogenated by the furan fragment of described replacement;
4) in the combination transfer of solvent and partially hydrogenated substituted furan to cycloaddition reaction device, the furan of described replacement and ethylene wherein will be made under described solvent exists when cycloaddition reaction and to react in the presence of a catalyst and prepare two cyclic ethers,
5), after, described two cyclic ethers dehydrations are produced the phenyl replaced under described solvent exists;
6) reclaim described solvent and described solvent is recycled to step 2; With
7) after, the phenyl of described replacement being oxidized to p-phthalic acid, the furan of wherein said replacement is represented by below formula:
Described two cyclic ethers are represented by below formula:
The phenyl of described replacement is represented by below formula:
Wherein R is=O, OH or OC (O) CH3, R*It is=O, OH, OC (O) CH3 or H,
But condition is R and the R on the furan of described replacement*Substituent group was not all hydrogenated to corresponding alkyl before described cycloaddition step.
27. the method for section 26, wherein Isosorbide-5-Nitrae-phenylene dimethanol is used as furan extraction and the solvent in ethylene cycloaddition/both dehydrations of described replacement.
28. the method for section 1, wherein:
1) furan of described replacement has the cycloaddition/dehydration reactor of gas phase and aqueous phase plus the supply of non-essential solvent, and described reactor contains catalyst;
2) ethylene is added in described reactions steps, and the gas phase from described reactor removes Excess ethylene;
3) vapor effluent stream is cooled down, and water is separated with unreacted ethylene vapor and any organic facies;
4) discharge water from system, and ethylene vapor is sent back to cycloaddition/dehydration reactor.
Predictability embodiment
Predictability embodiment 1:HMF converts to the on-catalytic of HMBA
100mL 1.0MHMF in 2-butanol is added the autoclave equipped with gas access, thermocouple, pressure transducer and magnetic stirring bar with 160mL volume. Described autoclave is sealed, at room temperature pressurizes with ethylene, and be heated to the reaction temperature of 250 DEG C. Make the reaction period that reaction runs 24 hours, maintain the ethylene pressure of 6200kPa in autoclave simultaneously. Then by reactor cooled the analysis obtaining product.
Predictability embodiment 2:BHMF converts to the on-catalytic of PMB
100mL 1.0MBHMF in 2-butanol is added the autoclave equipped with gas access, thermocouple, pressure transducer and magnetic stirring bar with 160mL volume. Described autoclave is sealed, at room temperature pressurizes with ethylene, and be heated to the reaction temperature of 250 DEG C. Make the reaction period that reaction runs 24 hours, maintain the ethylene pressure of 6200kPa in autoclave simultaneously. Then by reactor cooled the analysis obtaining product.
Predictability embodiment 3:HMF is to the catalyzed conversion of HMBA
Follow the experimental arrangement described in predictability embodiment 1, be different in that before pressurizeing with ethylene and the 0.5g solid catalyst being in granular form (pellet or powder) is added in reactor. Experiment describes in Table 1.
Table 1
Embodiment Catalyst Si/Al ratio Reaction temperature (DEG C) Reactant
A H-BEA 12.5 250 HMF
B H-BEA 19 250 HMF
C H-FAU 2.6 250 HMF
D H-ZSM-5 15 250 HMF
E Niobic acid 250 HMF
F γ-Al2O3 250 HMF
Predictability embodiment 4:BHMF is to the catalyzed conversion of PDM
Follow the experimental arrangement described in predictability embodiment 2, be different in that before pressurizeing with ethylene and the 0.5g solid catalyst being in granular form (pellet or powder) is added in reactor. Experiment describes in table 2.
Table 2
Embodiment Catalyst Si/Al ratio Reaction temperature (DEG C) Reactant
A H-BEA 12.5 250 BHMF
B H-BEA 19 250 BHMF
C H-FAU 2.6 250 BHMF
D H-ZSM-5 15 250 BHMF
E Niobic acid 250 BHMF
F γ-Al2O3 250 BHMF
Predictability embodiment 5:HMF is to the catalytic hydrogenation of BHMF
100mL 1.0MBHMF in 2-butanol is added the autoclave equipped with gas access, thermocouple, pressure transducer and magnetic stirring bar with 160mL volume. By 0.5g at γ-Al2O31%Pt on catalyst adds in described autoclave. Described autoclave is sealed, at room temperature by pressurized with hydrogen, and is heated to the reaction temperature of 150 DEG C. Make reaction run, maintain the Hydrogen Vapor Pressure of 2000kPa in autoclave simultaneously.When consuming monovalent hydrogen, by cooling down and decompress stopped reaction device. Then the analysis of product is obtained.
Predictability embodiment 6: BHMF is to the catalyzed conversion of PDM in various solvents
100mL 1.0MBHMF in solvent (referring to table 3) is added the autoclave equipped with gas access, thermocouple, pressure transducer and magnetic stirring bar with 160mL volume. The H-BEA catalyst of the Si/Al ratio that 0.5g has 12.5 adds described reactor. Described autoclave is sealed, at room temperature pressurizes with ethylene, and be heated to the reaction temperature of 250 DEG C. Make the reaction period that reaction runs 24 hours, maintain the ethylene pressure of 6200kPa in autoclave simultaneously. Then by reactor cooled the analysis obtaining product.
Table 3
Embodiment Solvent Catalyst Reaction temperature (DEG C) Reactant
A 2-butanol H-BEA(12.5) 250 BHMF
B Toluene H-BEA(12.5) 250 BHMF
C 1:1 toluene: 2-butanol H-BEA(12.5) 250 BHMF
D Methyl iso-butyl ketone (MIBK) H-BEA(12.5) 250 BHMF
E HMBA H-BEA(12.5) 250 BHMF
F PDM H-BEA(12.5) 250 BHMF
All documents described herein (include any priority documents and/or test procedure) and are incorporated herein, to the degree that they are not inconsistent with present disclosure, as long as but being incorporated herein not over reference in the initial any priority documents applied for or do not enumerate in submission document submitted to. Although from above-mentioned general introduction and particular it is readily apparent that have illustrated and described the form of the present invention, but may be made that various amendment without departing from the spirit and scope of the present invention. And it is therefore not desirable to the present invention is so limited. Similarly, term " comprising (comprising) " is thought and term " including (including) " synonym for Australia's law. Equally, whenever compositions, element or element group transitional term " comprising " above time, it should be understood that to further contemplate that there is transitional term " substantially by ... composition ", " by ... composition ", " be selected from " or " is, and " same combination before the compositions enumerated, element or each element or element group, vice versa. Therefore, term contained in term " comprising " " substantially by ... composition ", " be " and " by ... composition " and use " comprise " can use Anywhere " substantially by ... composition ", " be " and " by ... composition " replaces.

Claims (28)

1. the preparation method of p-phthalic acid, and with ethylene react in the presence of a catalyst when cycloaddition reaction and prepare two cyclic ethers including the furan making replacement, the phenyl of replacement is prepared by described two cyclic ethers dehydrations, afterwards, the phenyl of described replacement is oxidized to p-phthalic acid, and the furan of wherein said replacement is represented by below formula:
Described two cyclic ethers are represented by below formula:
The phenyl of described replacement is represented by below formula:
Wherein R is=O, OH or OC (O) CH3, R*It is=O, OH, OC (O) CH3Or H,
But condition is R and the R on the furan of described replacement*Substituent group was not all hydrogenated to corresponding alkyl before described cycloaddition step.
2. the process of claim 1 wherein that described cycloaddition reaction condition includes the temperature of about 100 DEG C-about 300 DEG C.
3. the process of claim 1 wherein that described catalyst includes activated carbon, silicon dioxide, aluminium oxide, zeolite molecular sieve or non-zeolite molecular sieve.
4. the method for claim 3, wherein said catalyst includes activated carbon.
5. the method for claim 4, wherein said activated carbon is pickling.
6. the process of claim 1 wherein that at least 6 in the carbon atom of described p-phthalic acid are derived from one or more renewable raw materials.
7. the process of claim 1 wherein that the furan of described replacement is obtained by the conversion of glucose or fructose.
8. the process of claim 1 wherein that the furan of described replacement includes 5 hydroxymethyl furfural.
9. the process of claim 1 wherein that the furan of described replacement includes 2,5-double; two hydroxymethylfurans.
10. the method for claim 7, the furan of wherein said replacement is obtained by glucose or fructose converting one-tenth 5 hydroxymethyl furfural.
11. the method for claim 10, wherein said 5 hydroxymethyl furfural with ethylene cycloaddition before be not converted into 2,5-dimethyl furans.
12. prepare the method based on carbohydrate of p-phthalic acid, including:
A hexose is changed into 5 hydroxymethyl furfural by ();
B () makes described 5 hydroxymethyl furfural and ethylene when cycloaddition reaction and react in the presence of a catalyst and prepare two cyclic ethers, then described two cyclic ethers dehydrations are prepared the compound represented by formula (I):
C the compound oxidation represented by formula (I) is prepared p-phthalic acid with oxygen by (); Wherein said 5 hydroxymethyl furfural was not converted into 2,5-dimethyl furan before step (b).
13. prepare the method based on carbohydrate of p-phthalic acid, including:
A hexose is changed into the double; two hydroxymethylfurans of 2,5-by ();
B () makes described 2,5-double; two hydroxymethylfurans when cycloaddition reaction with ethylene and react in the presence of a catalyst and prepare two cyclic ethers, then described two cyclic ethers dehydrations are prepared the compound represented by formula (II):
C the compound oxidation represented by formula (II) is prepared p-phthalic acid with oxygen by (); The double; two hydroxymethylfurans of wherein said 2,5-was not converted into 2,5-dimethyl furan before step (b).
14. the process of claim 1 wherein that the furan of described replacement is represented by below formula:
Described two cyclic ethers are represented by below formula:
The phenyl of described replacement is represented by below formula:
Wherein R*It is=O or-OH.
15. the method for claim 1,12,13 or 14, the furan of wherein said replacement includes 2,5-double; two hydroxymethylfurans, and described 2,5-double; two hydroxymethylfurans is combined with acid to prepare diester before described cycloaddition step.
16. the method for claim 15, wherein said acid is acetic acid.
17. the process of claim 1 wherein and added the hydrogen less than 1.5 moles for every monobasic Furan Molecules before described cycloaddition step.
18. the process of claim 1 wherein and added the hydrogen less than 1 mole for every monobasic Furan Molecules before described cycloaddition step.
19. the method preparing 1,4-CHDM, including:
A hexose is changed into the double; two hydroxymethylfurans of 2,5-by ();
B () makes described 2,5-double; two hydroxymethylfurans when cycloaddition reaction with ethylene and react in the presence of a catalyst and prepare two cyclic ethers, then make the compound that described two cyclic ethers dehydrations and preparing are represented by formula (II):
(c) include the base metal catalysts of Ni, Cu or noble metal Rh, Pt or many metallized metals catalyst exist under with hydrogen, the hydrogenation of compounds represented by formula (II) is prepared 1,4 cyclohexane dimethanol; The double; two hydroxymethylfurans of wherein said 2,5-was not converted into 2,5-dimethyl furan before step (b).
20. method, including:
A hexose is changed into the double; two hydroxymethylfurans of 2,5-by ();
B () makes described 2,5-double; two hydroxymethylfurans when cycloaddition reaction with ethylene and react in the presence of a catalyst and prepare two cyclic ethers, then make the compound that described two cyclic ethers dehydrations and preparing are represented by formula (II):
The double; two hydroxymethylfurans of wherein said 2,5-was not converted into 2,5-dimethyl furan before step (b).
21. the method preparing plastification composite, be combined with one or more diester compounds represented by below formula including by polar polymer:
OrWherein R is C1-C20Alkyl.
22. the method for claim 21, wherein said polymer includes polrvinyl chloride and polyethylene terephthalate polymer.
23. the method for claim 21, wherein said diester compound is derived from Isosorbide-5-Nitrae-benzene dimethanol and/or 1,4-CHDM, and described Isosorbide-5-Nitrae-benzene dimethanol is obtained as below:
A hexose is changed into the double; two hydroxymethylfurans of 2,5-by ();
B () makes described 2,5-double; two hydroxymethylfurans when cycloaddition reaction with ethylene and react in the presence of a catalyst and prepare two cyclic ethers, then described two cyclic ethers dehydrations are prepared the compound represented by formula (II):
Or 1,4 cyclohexane dimethanol is obtained as below: with hydrogen, the compound represented by formula (II) is hydrogenated further under base metal or noble metal (single or multiple metal) catalyst exist and prepare 1,4 cyclohexane dimethanol; The double; two hydroxymethylfurans of wherein said 2,5-was not converted into 2,5-dimethyl furan before step (b).
24. the preparation method of p-phthalic acid, including:
1) hexose changes into the furan of replacement in two-phase reactor, and described reactor has organic facies and aqueous phase;
2) organic solvent is used to extract the furan of described replacement from the material produced by described two-phase reactor;
3) in the combination transfer of solvent and the furan of replacement to cycloaddition reaction device, the furan of described replacement and ethylene wherein will be made under described solvent exists when cycloaddition reaction and to react in the presence of a catalyst and prepare two cyclic ethers,
4), after, described two cyclic ethers dehydrations are produced the phenyl replaced under described solvent exists;
5) reclaim described solvent and described solvent is recycled to step 2; With
6) after, the phenyl of described replacement being oxidized to p-phthalic acid, the furan of wherein said replacement is represented by below formula:
Described two cyclic ethers are represented by below formula:
The phenyl of described replacement is represented by below formula:
Wherein R is=O, OH or OC (O) CH3, R*It is=O, OH, OC (O) CH3Or H,
But condition is R and the R on the furan of described replacement*Substituent group was not all hydrogenated to corresponding alkyl before described cycloaddition step.
25. the method for claim 24, wherein (methylol) benzaldehyde is used as furan extraction and the solvent in ethylene cycloaddition/both dehydrations of described replacement.
26. the preparation method of p-phthalic acid, including:
1) hexose changes into the furan of replacement in two-phase reactor, and described reactor has organic facies and aqueous phase;
2) organic solvent is used to extract the furan of described replacement from the material produced by described two-phase reactor;
3) under described solvent exists, the furan of described replacement is combined with the relative each mole of furan the replaced hydrogen less than 2 moles to be hydrogenated by the furan fragment of described replacement;
4) in the combination transfer of solvent and partially hydrogenated substituted furan to cycloaddition reaction device, the furan of described replacement and ethylene wherein will be made under described solvent exists when cycloaddition reaction and to react in the presence of a catalyst and prepare two cyclic ethers,
5), after, described two cyclic ethers dehydrations are produced the phenyl replaced under described solvent exists;
6) reclaim described solvent and described solvent is recycled to step 2; With
7) after, the phenyl of described replacement being oxidized to p-phthalic acid, the furan of wherein said replacement is represented by below formula:
Described two cyclic ethers are represented by below formula:
The phenyl of described replacement is represented by below formula:
Wherein R is=O, OH or OC (O) CH3, R*It is=O, OH, OC (O) CH3Or H,
But condition is R and the R on the furan of described replacement*Substituent group was not all hydrogenated to corresponding alkyl before described cycloaddition step.
27. the method for claim 26, wherein Isosorbide-5-Nitrae-phenylene dimethanol is used as furan extraction and the solvent in ethylene cycloaddition/both dehydrations of described replacement.
28. the process of claim 1 wherein:
1) furan of described replacement has the cycloaddition/dehydration reactor of gas phase and aqueous phase plus the supply of non-essential solvent, and described reactor contains catalyst;
2) ethylene is added in described reactions steps, and the gas phase from described reactor removes Excess ethylene;
3) vapor effluent stream is cooled down, and water is separated with unreacted ethylene vapor and any organic facies;
4) discharge water from system, and ethylene vapor is sent back to cycloaddition/dehydration reactor.
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